Base induced isomerisation of a phosphaethynolato-borane: mechanistic insights into boryl migration and decarbonylation to afford a triplet phosphinidene.

Chemical Science
Daniel W N WilsonJose Manuel Goicoechea

Abstract

We report on the (tert-butyl)isocyanide-catalysed isomersation of a phosphaethynolato-borane, [B]OCP ([B] = N,N'-bis(2,6-diisopropylphenyl)-2,3-dihydro-1H-1,3,2-diazaboryl), to its linkage isomer, a phosphaketenyl-borane, [B]PCO. Mechanistic insight into this unusual isomerisation was gained through a series of stoichiometric reactions of [B]OCP with isocyanides and theoretical calculations at the Density Functional Theory (DFT) level. [B]PCO decarbonylates under photolytic conditions to afford a novel boryl-substituted diphosphene, [B]P[double bond, length as m-dash]P[B]. This reaction proceeds via a transient triplet phosphinidene which we have been able to observe spectroscopically by Electron Paramagnetic Resonance (EPR) spectroscopy.

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Citations

Jun 6, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Riccardo SuterHansjörg Grützmacher
Jun 9, 2020·Chemistry : a European Journal·Sebastian BestgenJose M Goicoechea
Jul 3, 2020·Angewandte Chemie·Daniel W N WisonJose Manuel Goicoechea
Dec 8, 2020·Physical Chemistry Chemical Physics : PCCP·Eugenii Ya MisochkoVasili A Miluykov
Apr 13, 2021·Angewandte Chemie·Stephan HagspielHolger Braunschweig
Oct 22, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Daniel W N WilsonJose M Goicoechea
Aug 5, 2021·Inorganic Chemistry·Akachukwu D ObiRobert J Gilliard
Sep 1, 2021·Angewandte Chemie·Grégoire Le CorreHansjörg Grützmacher
Sep 24, 2021·Angewandte Chemie·Doruk Ergöçmen, Jose M Goicoechea

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Methods Mentioned

BETA
NMR
X-ray
thermal dissociation
electron paramagnetic resonance

Software Mentioned

Gaussian09

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